Ammonium nitrate composition containing pyridazinedione combustion catalyst



United States Patent 3,154,447, Patented Oct. 27, 1964 3,154,447 AMMU NITRATE CUIVWGSITION CUN- TAINING PYRIDAZINEDIONE COMBUS- TION CATALYST Wayne A. Proell, Chicago, Ill., and Donald J. OConnor, Hammond, ImlL, assignors to Standard Gil Company, Chicago, Ill., a corporation of Indiana No Drawing. Filed Jan. 28, 1960, Ser. No. 5,584 3 Claims. (Cl. 1491) This invention relates to ammonium nitrate-type compositions and particularly a catalyst for promoting the combustion of ammonium nitrate containing compositions.

In gas generation and rocketry usages it is necessary that the gas affording composition develop gas at a uniform rate; in the art this is spoken of as burning at a uniform rate. In ammonium nitrate compositions which consist essentially of ammonium nitrate particles and an oxidizable organic material which permits the shaping of the composition into a definite configuration or grain is necessary to promote the combustion of the composition by the use of a combustion catalyst. The best known catalysts are the inorganic chromium compounds particularly, ammonium dichromate. In the military field the Prussian blues have attained eminence. These and other metallic catalysts have the drawback of forming oxides with very high melting points. It is thought that these solid oxide products in the combustion gases are the cause of nozzle erosion. Nozzle erosion results in erratic change in gas pressure within the gas generator or rocket motor.

An object of the invention is an ammonium nitrate composition. A particular object of the invention is an ammonium nitrate .composition having low erosive characteristics. A further object is an ammonium nitrate composition whose burning rate is relatively insensitive to variations in burning chamber pressure. Other objects will become apparent in the course of the detailed description.

It has been found that an eminently suitable ammonium nitrate-type composition for gas generator and rocketry usage is obtained with ammonium nitrate as the predominant component between about and 40 weight percent of oxidizable organic material and between about 0.5 and weight percent of an alkali metal salt of 1,2-dihydro- 3,6-pyridazinedione as the combustion catalyst. This catalyst burns to form products which have no appreciable nozzle erosive activity.

Sufiicient catalyst must be introduced into the composition to promote the burning of the composition. The amount of catalyst used is also influenced by the rate of burning desired. The more catalyst present the faster the combustion of the composition. It is to be understood that the burning rate is also affected by the particular oxidizable organic material present. In general, the composition will contain between about 0.5 and 15 weight percent of the catalyst. (Hereinafter all percentages are to be understood as weight percent.) With the thermoplastic matrix formers or binders obtained from cellulose esters and oxygenated hydrocarbon plasticizers therefor between about 1 and 6% of catalyst produces satisfactory burning rates for typical military gas generation and rocketry usages; more usually 2-4% is present.

The improved composition of the invention contains ammonium nitrate as the major component. The ammonium nitrate may be either ordinary commercial ammonium nitrate such as is used for fertilizers. This commercial grade material contains a small amount of impurities and the particles are usually coated with moisture resisting material such as parafiin wax. Military grade ammonium nitrate which is almost chemically pure is particularly suitable. The ammonium nitrate is preferably in a finely divided particulate form which may be either produced by prilling or by grinding. The ammonium nitrate is the major component of the gas-generator composition and usually the composition will contain between about 65 and of ammonium nitrate.

In order to permit the shaping of the ammonium nitrate composition into definite configurations a matrix former or binder material is present. When ammonium nitrate decomposes free-oxygen is formed. Advantage of the existence of this freeoxygen is taken and oxidizable organic materials are used as the binders. These oxidizable organic materials may contain only carbon and hydrogen, for example, high molecular weight hydrocarbons such as asphalts or residuums, and rubbers either natural or synthetic. Or, the oxidizable organic material may con tain other elements in addition to carbon and hydrogen for example Thiokol rubber and neoprene. The stoichiometry of the composition is improved, with respect to smoke production, by the use of oxygenated organic materials as the binders. The binder or matrix former may be a single compound such as a rubber or asphalt or it may be a mixture of compounds. The mixtures are particularly suitable when special characteristics are to be imparted to the grain which cannot be obtained by the use of a single compound.

The multi-component binder or matrix former commonly consists of a polymeric base material and a plasticizer therefor. Particularly suitable polymeric base materials are cellulose esters of alkanoic acids containing from 2 to 4 carbon atoms such as cellulose acetate, cellulose acetate butyrate and cellulose propionate; the polyvinyl resins such as polyvinylchloride and polyvinyl acetate are also good bases; styrene acrylonitrile is an example of a copolymer which forms a good base material. In general the binder contains between about 15 and 45% of the particular polymeric base material.

The plasticizer component of the binder is broadly defined as an oxygenated hydrocarbon. The hydrocarbon base may be aliphatic or aromatic or may contain both forms. The oxygen may be present in the plasticizer in ether linkage and/ or hydroxyl group and/ or carboxyl groups; also the oxygen may be present in inorganic substituents perticularly nitro groups. In general any plasticizer which is adopted to plasticize the particular polymer may be used in the invention. Exemplary classes of plasticizers which are suitable are set out below.

It is to be understood that these classes are illustrative only and do not limit the types of oxygenated hydrocarbons which may be used to plasticize the polymer.

Di-lower alkyl-phthalates, e.g., dimethyl phthalate, dibutyl phthalate, dioctyl phthalate and dimethyl nitrophthalate.

Nitrobenzenes, e.g., nitrobenzene, dinitrobenzene, nitrotoluene, dinitrotoluene, nitroxylene, and nitrodiphenyl.

Nitrodiphenyl ethers, e.g., nitrodiphenyl ether and 2,4-

dinitrodiphenyl ether.

Tri-lower alkyl-citrates, e.g., triethyl citrate, tributyl citrate and triamyl citrate.

Acyl tri-lower alkyl-citrates where the acyl group contains 2-4 carbon atoms, e.g., acetyl triethyl citrate and acetyl tributyl citrate.

Glycerol-lower alkanoates, e.g., monoacetin, triacetin,

glycerol tripropionate and glycerol tributyrate.

Lower alkylene-glycoLlower alkanoates wherein the glycol portion has a molecular weight below about 200, e.g., ethylene glycol diacetate, triethylene glycol dihexoate, triethylene glycol dioctoate, polyethylene glycol dioctoate, dipropylene glycol diacetate, nitromethyl propanediol diacetate, hydroxyethyl acetate and hydroxy propyl acetate (propylene glycol monoacetate).

Dinitrophenyl-lower alkyl-lower alkanoates, e.g., dinitrophenyl ethylacetate, and dinitrophenyl amyloctoate.

Lower alkylene-glycols wherein the molecular weight is below about 200, e.g., diethylene glycol, polyethylene glycol (200), and tetrapropylene glycol.-

Lower alkylene-glycol oxolates, e.g., diethylene glycol oxolate and polyethylene glycol (200) oxolate.

Lower alkylene-glycol maleates, e.g., ethylene glycol maleate and bis-(cliethylene glycol monoethyl ether) maleate.

Lower 'alkylene-glycol diglycolates, e.g., ethylene glycol diglycolate and diethylene glycol diglycolate.

Miscellaneous diglycolates, e.g., dibutyl diglycolate,

dimethylalkyl diglycolate and methylcarbitol diglycolate.

Lower alkyl-phthalyl-lower alkyl-glycolate, e.g., methyl phthalyl ethyl glycolate, ethyl phthalyl ethyl glycolate and butyl phthalyl butyl glycolate.

Di-lower alkyloxy-tetraglycol, e. g., dimethoxy tetra glycol and dibutoxy tetra glycol.

Nitrophenylether of lower alkylene glycols, e.g., dinitrophenyl ether of triethylene glycol and nitrophenyl ether of polypropylene glycol.

Nitrophenoxy alkanols wherein the alkanol portion is derived from a glycol having a molecular weight of not more than about 200. These may be pure compounds or admixed with major component bis(nitrophenoxy) alkane.

A single plasticizer may be used or more usually two or more plasticizers may be used in conjunction. The particular requirements with respect to use will determine not only the polymer but also the particular plasticizer or combination of plasticizers which are used.

In addition to the basic components, i.e., ammonium nitrate binder and catalyst, the gas-generator propellant composition may contain other materials. For example, materials may be present to improve low temperature ignitability, for instance oximes may be present or, asphalt may be present. Surfactants may be present in order to improve the coating of the nitrate with the binder and to improve the shape characteristics of the composition. Various burning rate promoters, which are not catalyst per se, may also be present.

The aromatic hydrocarbon amines are known to be gas evolution stabilization additives. Examples of these aromatic amines are toluene diamine, diphenyl amine, naphthalene diamine, and toluene triamine. In general the aromatic hydrocarbon amines are used in amounts between about 0.5 and percent. While these aromatic hydrocarbon amines are effective, for severe duties they are frequently not sufi'iciently effective alone. It has been found that extremely good stabilization is obtained when N-phenylrnorpholine additive is used with an aromatic hydrocarbon amine. Because of the plasticizing power of the N-phenylmorpholine it is generally desirable to use the aromatic hydrocarbon amines as the primary stabilizing additive and the N-phenylmorpholine in an amount needed to obtain the specific stability. In general when aromatic hydrocarbon amines are present between about 0.1 and 1 percent of N-phenylmorpholine will be used.

, Broadly the composition will contain between about 20 and 35 Weight percent of binder when the polymeric base material is a cellulose ester of an alkanoic acid containing 2 to 4 carbon atoms and an oxygenated hydrocarbon plasticizer therefor. A particularly useful composition consists of cellulose acetate, about 812%; ace- 25. tyltriethylcitrate, about 8-12%; on about 2:1 mixture of dinitrophenoxyethanol and bis(di-nitrophenoxy) ethane, about 8l2%; carbon, about 24%; toluene diamine, about 1% and catalyst, about 24%.

Test

The composition to be tested for burning rate, pressure exponent and other characteristics required by military specifications was prepared by first forming a homogeneous viscous liquid binder at a temperature of about 130 C. Lacquer grade commercial cellulose acetate analyzing about 55% of acetic acid was the polymer base. Two plasticizers were used. The one plasticizer contained about 2 parts of dinitrophenoxy ethanol and 1 part of bis(dinitrophenoxy) ethane. This plasticizer mixture was obtained naturally by the reaction of dinitrochlorobenzene and ethylene glycol in the presence of aqueous sodium hydroxide solution. The other plasticizer was acetyl triethyl citrate. The binder was then cooled to about C. and the ammonium nitrate in fine particles, carbon black and toluene diamine was blended into the binder until a pasty mass was formed. At this time sodium l,2-dihydro-3,6-pyridazinedione was introduced into the mixture and worked into the mass of material. The homogeneous pasty mass was extruded as rods suitable for use in burning rate tests. Other portions were molded into gas-generator grains for use in large size gas-generation tests. The burning rate tests were conducted in a Crawford bomb pressured at 1000 p.s.i. and 25 C. temperature.

The composition consisted of cellulose acetate 10%, the dinitrophenoxy mixture 10.2%, acetyl triethyl citrate 9.8%, carbon black 3%, toluene diamine 1%, ammonium nitrate 63%, and catalyst 3%. burning rate of 0.103 inch per second and a pressure exponent of 0.53.

Thus having described the invention, what is claimed is: 1. A composition consisting essentially of between about 0.5 and 15 weight percent of an alkali metal salt of 1,2-dihydro-3,6-pyridazinedione combustion catalyst, ammonium nitrate as the predominate component and between about 10 and 40 weight percent of oxidizable organic binder material wherein said binder material consists of a polymeric base selected from the class consisting of cellulose esters of alkanoic acids containing from 2 to 4 carbon atoms, polyvinyl chloride, polyvinyl acetate, and styrene-acrylonitrile, and an oxygenated hydrocarbon adapted to plasticize said polymer.

2. A composition consisting essentially of ammonium nitrate as the predominant component, between about 1 and 6 weight percent of an alkali metal salt of 1,2-dihydro- 3,6-pyridazinedione, between about 20 and 35 Weight percent of a binder consisting of a cellulose ester of an alkanoic acid containing 2 to 4 carbon atoms and an oxygenated hydrocarbon adapted to plasticize said polymer.

3. A composition consisting of (a) ammonium nitrate, (b) cellulose acetate, about 8-12%, (0) acetyl triethyl citrate, about 8l2%, (d) about 812% of an about 2:1 mixture of dinitrophenoxyethanol and his (dinitrophenoxy) ethane, (e) carbon, about 24%, (1) toluene diamine, about 1% and (g) sodium salt of 1,2-dihydro-3,6-pyridazinedione, about 24%.

No references cited.

This composition had a 

1. A COMPOSITON CONSISTING ESSENTIALLY OF BETWEEN ABOUT 0.5 AND 15 WEIGHT PERCENT OF AN ALKALI METAL SALT OF 1,2-DIHYDRO-3,6-PYRIDAZINEDIONE COMBUSTION CATALYST, AMMONIUM NITRATE AS THE PREDOMINATE COMPONENT AND BETWEEN ABOUT 10 AND 40 WEIGHT PERCENT OF OXIDIZABLE ORGANIC BINDER MATERIAL WHEREIN SAID BINDER MATERIAL CONSISTS OF A POLYMERIC BASE SELECTED FROM THE CLASS CONSISTING OF CELLULOSE ESTERS OF ALKANOIC ACIDS CONTAINING FROM 2 TO 4 CARBON ATOMS, POLYVINYL CHLORIDE, POLYVINYL ACETATE, AND STYRENE-ACRYLONITRILE, AND AN OXYGENATED HYDROCARBON ADAPTED TO PLASTICIZE SAID POLYMER. 